Borate esters prepared by successive reactions of boric acid with glycol

ABSTRACT

Borate esters of the formula:   WHERE R1 and R2 are hydrogen or methyl; R3 and R4 are each an independently selected alkyl group having from 1 to 20 carbon atoms; R5 is the organic residue exclusive of reactive hydroxyl groups of a polyol, p is an integer of from 2 to 6 inclusive and n and m are positive integers independently selected in each chain and whose sum in each chain is from 2 to 20 are prepared by successively reacting boric acid with a glycol monoether and a polyol. These esters are useful as stabilizers and corrosion inhibitors for lubricants and non-aqueous hydraulic fluids.

United States Patent 1 [1 1 B 3,914,275

Sawyer et al. Oct. 21, 1975 BORATE ESTERS PREPARED BY 3,527,765 9/1970Reece et al. 260/462 R x SUCCESSIVE REACTIONS OF BORlC ACID WITH GLYCOLPrimary Examiner-Leon Zitver Assistant Examiner-Norman P. Morgenstern[75] Inventors. Arthur W. Sawyer Hamden; David A. csejka orangboth ofCon Attorney, Agent, or FzrmKenneth P. Glynn; Eugene Zagarella, Jr. [73]Assignee: Olin Corporation, New Haven,

Conn 57 ABSTRACT [22] Flled: 1973 Borate esters of the formula: [21]Appl. No.: 328,210

. OCH C} C [44] Published under the Trial Voluntary Protest Bag 2 mill(0 H2CHR2)n97\ Program on January 28, 1975 as document no. B 0 R, B328,210 R H0CH2CHB -(OCHgCHRg) Q7 Related US. Application Data 1;Division of f- P- ,5 9 1970, where R, and R are hydrogen or methyl; Rand R 3329,4973 whlch a dlvlslo of Sen 653,337, are each anindependently selected alkyl group having July 1967 3537794 A from 1 to20 carbon atoms; R is the organic residue exclusive of reactive hydroxylgroups of a polyol, p is [52] US. Cl; 260/462 R i an integer of from 2to 6 inclusive and n and m are [5 I] lift. Ci. positive integersindependently selected in each chain Fleld Of Search R and whose sum ineach Chain is from 2 to are p pared by successively reacting boric acidwith a glycol [56] Reierences cued monoether and a polyol. These estersare useful as sta- UNITED TATE PATENTS bilizers and corrosion inhibitorsfor lubricants and 3,080,412 3/ 1963 Young 260/462 R non-aqueoushydraulic fluids. 3,129,239 4/1964 Lang 260/462 R 3,303,130 2/1967Scypinski et al. 260/462 R x 2 Clalms, N0 Drawmgs mixture of glycolmonoethers to yield an intermediate borate compound (A). Secondly, theintermediate borate compound is reacted with a polyol having from 2 to 6inclusive hydroxyl groups to obtain the novel borate compounds (B) ofthe present invention. The two reactions, namely the reaction of thefirst stage and the reaction of the second stage, proceed as shown inthe following equations where for purposes of illustration a singleglycol monoether is utilized in preparing compound (A):

I. 2 REOCH CHRQ -(OCH CHRQQOH H3B03 l -OH(A) R ioCll CHRfl (OCl-l CHR Ozn o "it (ocu cna -(OCH2CHR2) 0 I: m :13 OH ama)?" R (OCHZCHRI)-(OCH2CHR2) 0 p t lYoca ctmg (OCHZCHRQHQ L p520 R EOCH CHR (OCHZCHRQHCZ'where R and R are independently selected from the group consisting ofhydrogen or methyl; R and R are each an independently selected alkylgroup having from 1 to carbon atoms; R is the organic residue exclusiveof reactive hydroxyl groups of a polyol, p is an integer of from 2 to 6inclusive and n and m are positive integers independently selected ineach chain and whose sum in each chain is from 2 to 20.

The novel borate esters of this invention are useful as desiccants fordrying of gases and as stabilizers and corrosion inhibitors forlubricants and non-aqueous hydraulic fluids, such as those based onglycols, polyglycols, the alkylene oxide adducts of phenols and thedialkyl ethers of glycols and polyglycols.

The novel esters of this invention are stable at elevated temperaturesand they possess very high boiling points. On hydrolysis these novelborate esters yield ultimately the glycol monoether, boric acid and thepolyol employed in preparing these compounds.

The novel borates of this invention are also useful as ingredients insoldering of brazing fluxes. They also find use as compoundingingredients for natural and synthetic resins, since in addition toserving as plasticizers, they reduce the flammability of the materialbeing plasticized.

In general, the novel compounds of this invention are prepared in twosteps. In the first step, a stoichiometric amount of a boron-containngcompound, such as orthoboric acid, is reacted with a glycol monoether orwherein R R R n, m and p have the same meaning as previously describedand R is alkyl of from 1 to 20 carbon atoms.

In the preferred method of preparation boric acid is employed as theboron-containing material and an inert water-azeotroping solvent isadded to the reaction vessel along with the glycol monoether startingmaterial. The water-azeotroping solvent is selected so that theazeotrope distils at a temperature below the boiling point of themonohydroxy compound. The temperature of the reaction mixture isinitially maintained preferably between 0 and 200C. and desirably at thedistillation temperature of the water-solvent azeotrope. The use of agraduated Barrett receiver facilitates the measurement and separation ofthe water of condensation.

Preferably, the reaction is conducted without an added catalyst tosimplify the utilization of the product, although an esterificationcatalyst may be employed, if desired. When the water removed isequivalent to the stoichiometric requirement to yield the intermediateborate compound (A), the reaction mixture is cooled to a temperaturebelow its reflux temperature and a stoichiometric amount of a polyolbridging compound is introduced into the reaction mixture. Afterstirring the mixture to ensure unifonnity, it is again heated so thatazeotropic removal of water is resumed. As soon as the removal of wateris essentiallycompleted, the solvent is then conveniently removed bydistillation. The borate ester remaining after removal of the solventcan be further stripped under reduced pressure to remove any unreactedstarting materials present. Other methods are known in the art forpurifying the borate ester. For example, the ester can be recovered asthe pure product by extraction with a suitable solvent followed byevaporation of the solvent.

Boron compounds which are suitable as starting materials for thepreparation of the novel boron esters include orthoboric acid, metaboricacid, boric oxide, and the like. Orthoboric acid, metaboric acid andboric oxide are preferred because of their relatively low cost. Tolueneand benzene are the preferred azeotropeforming solvents; however, otherinert solvents may be utilized providing that they form azeotropes withwater, such as, for example, xylene, ethylbenzene, mesitylene and thelike.

Glycol monoethers suitable for use in the preparation of the novelborate esters of this invention include those of the formula:

where R and R are independently selected from the group consisting ofhydrogen and methyl, R is an alkyl group containing from 1 to carbonatoms, and m i and n are positive integers whose sum is from 2 to 20.

Many glycol monethers are commercially available,

Suitable glycol monethers for example, include:

. CH (OCH CHCH OH C H (OCH CHCH (OCH CH )OH also be used. Polyolssuitable for use in connecting two CH3 (OCH2CH2)30 /BO CH3 ocu cng o 1or more of the intermediae borates of the formula:

R Economy (OClbCHRfi l R EOCH CHR toca cimg g wherein R R R R.,, m and nhave the same meaning as previously described, include compounds of theformula:

wherein P is an integer of from 2 to 6 inclusive and wherein R is theorganic residue exclusive of the reactive hydroxyl groups. Usefulpolyols include l) glycols of the formula:

wherein R is alkylene of from 2 to 10 carbon atoms and r is an integerof from 1 to 10; (2) thioglycols selected frop the group consisting ofthiodiethylene glycol and thiodipropylene glycol; (3) amines of theformula:

wherein s is an integer of from 2 to 3 inclusive, 2 is an integer offrom 1 to 10 inclusive, R is selected from the group consisting ofhydrogen and methyl and R is selected from the group consisting ofhydrogen and alkyl of from 1 to 4 carbon atoms and (4) polyols havingfrom 3 to 6 inclusive hydroxyl groups.

Specific examples of the above-mentioned polyols include for example,ethylene glycol, propylene glycol, butylene glycol, isobutylene glycol,pentanediol, hexylene glycol, neopentyl glycol, diethylene glycol,tetraethylene glycol, hexaethylene glycol, decaethylene glycol,dipropylene glycol, triisopropylene glycol, tetrapropylene glycol,hexabutylene glycol, 2-ethyl-l,3- hexanediol, thiodiethylene glycol,thiotripropylene gly col, diethanolamine, dipropanolamine,triethanolamine, tributanolamine, methyl diethanolamine, ethyldiethanolamine, methyl dipropanolamine, ethyl dipropanolamine, methyldibutanolamine, propyl dipropanolamine, butyl diethanolamine, glycerol,trimethylol propane, pentaerythritol, sorbitol, mannitol and1,2,6-hexanetriol.

The novel borate esters of this invention can be utilized to preparebrake fluid having boiling points in excess of 490 F. In such brakefluid compositions these borates form the major component and arepresent in amounts of from about to about per cent by weight of thefinal fluid. A typical hydraulic fluid composition utilizing the productof Example V, which has the formula:

0 gca cn m cn is given below: As soon as the water had been essentiallyall removed, Per Cent the toluene was distilled off and the residuecontaining by weight the product was stripped under water aspiratorvacuum Product of Example v 75.0 5 at 90 to 120C. pot temperature for1.5 hours in i l? mommethy' ether 23 order to remove unreacted products.A total of l 192 g. Polyethylene glycol (Mol. wt 200) 15.0 of product(essentially 100 per cent of theory), a clear Sodium Nitrite colorlessliquid with a viscosity at 40C. of approximately 1400 cs and having theformula:

This formulation was tested in accordance with the was obtainedappropriate methods of the SAE 170C for Hydraulic Brake Fluids and thefollowing properties were, observed: 25 Reflux Boiling Point 509FAnalyss B Viscosity at 212F 2.7 c

at 40F 3380 c5 Calculated: 2.72 Cold Test 6 days at 40F clear liquidFound: 2.78

6 hours at 58F clear liquid Rubber Swelling (Natural Rubber, 2.5diameter 120 hours 158F (Styrene-butadiene, 4.2% diameter 70 hours. 248FWater Tolerance (3.5 per cent vol. EXAMPLE H added water) 24 hours at40F. clear li uid 24 hours at [40F clear g In a manner similar to thatin Example 1, 242.7 g. (2

moles) of CH (OCH CH OH, 61.85 g. (1 mole) or- These values illustratethe highly superior properties thoborrc acid and 230 ml. toluene weremixed together of hydraulic fluids prepared with the novel borates ofthis invention. The addition of 3.5 per cent volume of and heated atreflux temperature until 36 moles) water to the above formulationyielded a fluid having of water had been removed as the azeotrope. Thereaca reflux boiling point of 368F. according to the procetion mixturewas allowed to cool below reflux temperadure of ASTM 1120-65, whereastypical currently 40 tue and 53.6 g. (0.5 mole) of diethylene glycol wasincommercial brake fluids with P cent added Water troduced, withcontinued stirring. The mixture was rehave inferior (i.e., below 302F.when tested in the heated to resume t o ing action. When water Samemannerseparation essentialy had ceased, the toluent was dis- Thefollowing examples illustrate specific embodiments of this invention andare to be considered not limitative:

tilled off and the residue was stripped under full water aspiratorvacuum at a pot temperature of 138 to 140C. for 10 minutes to removeunreacted starting EXAMPLE I materials. Product in the amount of 291 g.(96 per cent A total of 985 g. (6mo1es) of CH OCH CHQ OH, of thetheoretical yield), a clear, light straw-colored liq- 1355 g- (3 0leS)of orthoboric acid and 510 f uid, was obtained. This product, which hasthe formula:

CH3 (OCHZCHQZO o (ca cu m cu uene were mixed together in a 2 liter,round-bottom, exhibited a viscosity at 40C of 3632 cs. 3-neck flaskequipped with a magnetic stirrer. With I Analysis Per Cent heating atreflux temperature and stlrrlng, the water of condensation was removedas formed by azeotropic ac- C H B tion. When 108 ml. (6 moles) of waterhad separated, Calculated, 4736 310 3.59 the reaction mixture wasallowed to cool below reflux 5 nd: 46.76.46.49 8.46,8.70 3.57.3.60

temperature. Then 179 g. (1.5 moles) of 2-methyl-2,4-

pentanediol was introduced and the reaction mixture EXAMPLE was stirredand reheated to reflux temperature in order In a m nn i il to E l I, 3242 l to resume azeotroping out the water of condensation. of CH (OC1-1,CHOH, 61.8 g. (1 mole) of orthoboric acid and 265 ml. of toluene weremixed together and heated until a total of 36 ml. (2 moles) of water hadbeen removed as the azeotrope. 45.4 g. (0.33 mole) of commercialtrimethylol propane was introduced into the hot liquid. As soon as thesolid trimethylol propane flakes had dissolved in the stirred reactionmixture, azeotropic removal of water was resumed. When separation ofwater had essentially ceased, the toluene was distilled off and theresidue was stripped at 140 to 148C. pot temperature under full wateraspirator vacuum for approximately minutes. A total of 375.4 g. (99.5percent of theoretical yield) of a clear, colorless liquid having theformula:

was obtained. The product exhibited a viscosity of 40C. of 6161 cs.

Analysis: Per Cent B Calculated: 2.88 Found: 2.87

EXAMPLE IV In a manner similar to the preceding examples, 324 g. (2moles) of CH (OCH CH OH, 61.8 g. (1 mole) of boric acid and 275 ml. oftoluene were mixed together and heated with continuous stirring until 36ml. of water had been removed as the azeotrope. Then 30.4 g. (0.17 mole)of sorbitol was introduced and azeotroping was continued untilseparation of water had essentially ceased. After the toluene had beendistilled off, the residue was stripped under full water aspiratorvacuum at a pot temperature of to 155C. for approximately 10 minutes toremove unreacted starting materials. A total of 360 g. of product (97per cent of theory), a clear, colorless liquid, having the formula:

odm ca m ca was obtained. The viscosity of the product at 40C. was11,827 cs.

In a manner similar to Example 1, 641.3 g. of commercial (99 per cent)CH (OCH CH OH, 164.9 g. orthoboric acid and 200 ml. of toluene weremixed together and heated. Simultaneously, the water of condensationformed was removed overhead as the watertoluene azeotrope. Afteressentially 5.33 moles of water had been removed, the reaction mixturewas allowed to cool below reflux temperature following which 82.7 g. of99 per cent glycerine was added. Azeotropic removal of water wasresumed. As soon as the water separation had essentially ceased, thetoluene was removed by distillation and the remaining reaction mixturestripped under full aspirator vacuum at a pot temperature of 145 to C.for 15 minutes to remove unreacted starting materials. Borate ester inthe amount of 734 g. (98.5 per cent of the theoretical yield), a clear,light straw-colored liquid, having the formula:

own cu m cu ca e-B CHO-B ca e-B (0142 ca m cn cu (OCH3CH2)2O wasobtained.

Analysis: Per Cent B Calculated: 3.88 Found: 4.17

EXAMPLE VI In a manner similar to Example III, a lower homolog,specifically CH [OCH,CH OH was substituted, using the same molar ratiosof other reactants as were used in Example III, to yield a clear,light-colored product (96 percent of theoretical) having a formula:

CHz'U'B Example I was repeated using a lower homolog, specifically CH(OCI-I CI-I OI-I, with the same molar ratios of other reactants, toyield a clear colorless liquid product (97 per cent of theory) havingthe following formula:

otcn crr co cizr The viscosity of the product at minus C. wasapproximately 450 cs.

Analysis: Per Cent B Calculated: 3.52 Found: 3.66

EXAMPLE VIII In a manner similar to preceding examples, 324 g. (2m0les)of CH (OCH CI-I OH, 61.8 g. (1 mole) orthoboric acid and 250 ml.of toluene were mixed together and heated with continuous stirring until36.5 ml. of water was removed as the azeotrope. Then 34.4 g.

(0.25 mole) of pentaerythritol was introduced and stirred until itdissolved. Azeotropic removal of water was continued and an additional17 ml. of water was removed and recovered. The mixture was then strippedunder full water aspirator vacuum while heating to 154C. pot temperatureto remove the toluene and any unreacted starting materials. A total of364.5 g. of product (99.5 per cent of theoretical) an essentially clearcolorless liquid with a viscosity at *40C. of 91 17 cs., having theformula:

ca ca 0) CH 2 2 3 3 0-3 0(CH2CH2O) cn CH3 (OC2H2)3O\ e21 0 (CH2CH2O)3CH3B0-CH2C-CH2OB\ CH3 (oc u ho 0 (CH2CH2O)3CH3 ml. of toluene were mixedtogether and heated with stirring until 36 ml. of water had beenseparated. Net 54.65 g. (0.5 mole) of diethanolamine was introduced wasobtained.

Anal sis: Per CentB y and azeotropic removal of water was continuedover- Calculated: 2.92 night. The reaction mixture was stripped underfull Found: 2.96

water aspirator vacuum, with stirring and heating to a pot temperatureof 143C to remove all toluene and un- EXAMPLE IX In a manner similar tothe preceding examples, 242. g. (2 moles) of commercial CH (OCI-I CI-IOH, 61.84 g. (1 mole) boric acid and 220 ml. toluene were mixed togetherand heated with continuous stirring until 36 reacted volatile startingmaterials. The resultant product, which weighed 281 g. (93 per cent oftheoretical), was a clear, light-brown liquid with a viscosity at C. ofapproximately 15,500 cs. and having the following formula:

CH3 (OCH2CH2)20 'O(CH2CH20)2CH3 CH3 (ocu cii a o H o(cii cir,0 ci1 ml.of water had been removed as the azeotrope. Then 61.9 g. 0.5 mole) ofcommercial thiodiethylene glycol 40 Analy was introduced. Azeotropicremoval of water was con- C H B N tinued until separation of water hadessentially ceased. After stripping the product under full wateraspirator vacuum to a pot temperature of 159C., to remove toluene andunreacted volatile materials, 298.5 g. (96.8 5 per cent of theoretical)of clear yellow-brown liquid product was obtained. The product whichexibited a viscosity at 40C. of 5200 cs., has the formula:

Per Cent Calculated 47.9 8.87 3.60 2.33 Found 46.92.46.96 8.77.8.54 3.622.55.2.65

EXAMPLE XI In a manner similarto Example IX, 2 moles of CH (OCI-I CI-IOl-l, 1 mole of orthoboric acid and 220 0- (CH2CH2O)2CH3 CH3 (ocn cn ho0- (CH2CH2O)2CH3 ml. toluene were mixed together and heated with stir-Analysis: Per Cent ring until 36 ml of water had been separated. Next61.77 g. (0.5 mole) of methyl diethanolamine was introduced andazeotropic removal of water was contin- Calculated 46.62 8.48 3.50 5.19ued overnight. The reaction mixture was then stripped Fund 459M6068173-36 under full water aspirator vacuum, with stirring and heating toa pot temperature of 140C. There was ob- EXAMPLE X tained 301 g. ofproduct (98 per cent of theoretical), In a manner similarto Example IX,2 moles of a clear, brown liquid with a viscosity at 40C. of 1783 CH(OCII Cl-I OH, 1 mole of orthoboric acid and 220 cs. and having theformula:

C H B S CH3 CH3 pentanediol was introduced and azeotropic removal ofAnalysis Per Cent water was resumed and continued essentialy to cessa- CH B N tion. The prgduct was then stripped to a pot temperature at 172 C.under full water aspirator vacuum to Calculated 48.79 9.01 3.52 2.28yield 208.3 g. (97 per cent theory) of a clear, colorless Found47.04,46.7l 8.7l,8.80 3.35 2.49,2.6l

liquid product having the formula:

c a (oci-i cit oca cuca m O(CH Cl-ICH 0CII CH O)C H c 11 (oca cu ocucaca m O(CH CHCH OCH CIl- O)C H CH3C-CH2-CHCH3 EXAMPLE XII A total of592 g. (4 moles) of CH (OCHCH CH OH, 123.7 g. (2 moles) of orthoboricacid and 325 ml. toluene were mixed and heated together while si- At40C. the product was a clear liquid.

multaneously 72 ml. of water was removed as the azeo- Analysis: Per CentB trope. Then 1 18.2 g. (1 mole) of 2-methyl-2,4- Calculated: 250pentanediol was introduced and the azeotropic re- Found: 2.61 moval ofwater was continued overnight, at which time the separation of wateressentially had ceased. The reaction mixture was stripped under fullwater aspirator EXAMPLE XIV vacuum while heating to a pot temperature of140C. to remove the toluene and any unreacted volatile startingmaterials. Product was recovered in the amount of methyl ethers with anaverage molecular weight of 186 704 g. (97 per cent of theoretical), aclear, yellow liq- (calculated from determined hydroxyl number of 301)uid having the formula was employed as a reactant in this experiment.The

A mixture of homologous polyethylene glycol monocu mcu caca o 0(CHSCHCHZO) 2(JH3 c11 -c-ci -ci-i-c1 lowest molecular weight componentof this mixture was triethylene glycol monomethyl ether and the averagefonnula of the mixture was:

The product was a clear liquid at 40C. I

Analysis: Per Cent B Calculated: 2.98 3( 2 2 )a.5 Found: 3.10

784 g. (4 moles) of this mixture and 123.7 g. (2 moles) of USP boricacid were reacted in toluene, in the manner of previous examples, until72 ml. (4 moles) of water had been removed as the azeotrope.

EXAMPLE XIII A sample of commercial butoxy ethoxy propanol wasdistilled, discarding approximately 10 per cent forecut andapproximately 20 per cent tail cut. 177 g. (1 mole) of the main (center)cut of colorless butoxy ethoxy propanol, 30.9 g. (0.5 mole) of boricacid and 200 ml. of

Then ll9 g. (1 mole) of hexylene glycol was introduced and azeotropicremoval of water was resumed and continued essentially to cessation.Stripping under vacuum to 163C. pot temperature in the manner of otherexamples, yielded 914 g. (99.5 per cent of theoretical) of a clear,light-yellow product having the formula:

15 CH; (ocn ca o At 40C. the product was a clear liquid.

In a manner similar to the preceding examples; 324 g. (2 moles) of CH(OCH Cl-l Ol-l, 61.8 g, (1 mole) ,oma cn m ea,

clear colorless liquid. This oxypropylated product was found to have ahydroxyl number of 123, a calculated average molecular weight of 456 andthe average for- 5 mula to be:

CH21(OCH2CHCH3 )5.1

In a manner similar to previous examples, 456 g. (1 mole) of aboveoxypropylated product, 30.9 g. (0.5 mole) of orthoboric acid and 200 ml.of toluene were mixed and heated together until 18 ml. (1 mole) of waterhad been recovered as the azetrope. 29.6 g. (0.25 mole) of2-methyl-2,4-pentanediol was then introduced. Azeotroping was resumedand continued overof orthoboric acid and 250 ml. of toluen w r i d nightat which time water separation had essentially and heated together until36 ml. (2 moles) of water was separated as the azeotrope. A total of54.3 g. (0.5 mole) of 2,2-dimethyl-1,3-propanediol was then introduced.Azeotropic removal of water was resumed and ceased. The product wasstripped to a pot temperature of 138C. under vacuum as in previousexamples. A total of 490 g. of a colorless, liquid product (essentially100 per cent of theory), a clear, viscous liquid at continued untilwater removal essentially ceased. The -C., having the formula:

(3 5 (oca cncii 0 c' ii tocn caca 0 product was stripped to a pottemperature of 165C.

0(CH3CHCH2)5 c 11 CH3-C-CH2-CH-CH3 was obtained.

under vacuum as in the previous examples. Product in Analysis; p Cent 5the amount of 374 g. (97 per cent of theoretical), a clear colorlessliquid product having a viscosity of 1605 g fi cs. at 40C. and havingthe formula:

CH (OCH Cl-l 0\ O(CH CH O CH B-OCH C (CH CH O13 CH (OCH CH 0 O(CH CH O)CH was recovered.

Analysis: Per Cent B Calculated: 2.79 Found: 2.82

EXAMPLEXVI Commercial isodecanol was oxypropylated by conventionaltechniques by charging isodecanol and an alkaline catalyst to a pressurereactor and then introduc- 6 ing propylene oxide under conditions whichyielded a What is claimed is:

l. A borate ester of the formula:

where R and R are independently selected from the lected from the groupconsisting of thiodiethylene glygroup consisting of hydrogen and methyl;R and R are col and thiodipropylene glycol and n and m are positive eachan independently selected alkyl group having integers whose sum is from2 to 20.

from 1 to carbon atoms; R is the organic residue exclusive of reactivehydroxyl groups of a thioglycol se- 2. A borate ester of claim 1 havingthe formula:

s TED STATES PATENT OFFICE CETIFICATE ()F CORRECTION Patent No. 3 DatgdOctober 2].,

Inventm-(S) Arthur W. Sawyer and David A. Csejka It is certified thaterror appears in the above identified patent and that said LettersPatent are hereby corrected as shown below:

On the cover page, the title of the invention should read --BORATEESTERS PREPARED BY SUCCESSIVE REACTIONS OF BORIC ACID WITH GLYCOLMONOETHERS AND POLYOLS.

At the top of column 1, the title of the invention should read -BOR.ATEESTERS PREPARED BY SUCCESSIVE REACTIONS OF BORIC ACID WITH GLYCOLMONOETHERS AND POLYOLS--.

Column 1, line 69 "boron-containng" should read boroncontaining.

Colunm 3, (formula 18) the formula should read --C H (OCH CH 3 (OCH CHCH0E" Column 4, line 22 the word "frop" should read --from.

Column 4, line 26 the generic formula should read [H (OCH CHR :l N (RColumn 6 lines 39-40 the word "temperatue" should read -temperature-.

Column 6 line 42 the word "axzeotroping" should read azeotroping.

Column 6 line 43, the Word "essentialy" should read essentially.

Column 6 line 43, the word "toluent" should read toluene-.

Column 12, line 66, the temperature L+0'C," h ld d LFOOC Signed andScaled this sixth D y Of Aprill976 Attest:

RUTH C. MASON A [testing Officer C. MARSHALL DANN ummissiuner oj'Parenrsand Trademark

1. BORATE ESTER OF THE FORMULA
 2. A borate ester of claim 1 having theformula: